EP0172040A1 - Verfahren zur Herstellung von einem hoch Oktan-Kohlenwasserstoffenschnitt durch Etherifierung von Olefinen - Google Patents

Verfahren zur Herstellung von einem hoch Oktan-Kohlenwasserstoffenschnitt durch Etherifierung von Olefinen Download PDF

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Publication number
EP0172040A1
EP0172040A1 EP85401133A EP85401133A EP0172040A1 EP 0172040 A1 EP0172040 A1 EP 0172040A1 EP 85401133 A EP85401133 A EP 85401133A EP 85401133 A EP85401133 A EP 85401133A EP 0172040 A1 EP0172040 A1 EP 0172040A1
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EP
European Patent Office
Prior art keywords
methanol
etherifiable
residual
hydrocarbons
olefin
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Granted
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EP85401133A
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English (en)
French (fr)
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EP0172040B1 (de
Inventor
Bernard Torck
Pierre Amigues
Yves Glaize
Henri Grangette
Jean Laurent
Fred Fitoussi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Elf Antar France
IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
Elf France SA
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Publication of EP0172040A1 publication Critical patent/EP0172040A1/de
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the invention relates to a method which makes it possible to increase the octane numbers of unsaturated gasolines, in particular cracked gasolines.
  • Light cracked essences contain a significant amount of olefins, for example from 30 to 40%, among which tertiary olefins, isoamylenes, isohexenes and isoheptenes.
  • these tertiary olefins can be converted into ethers by reaction with an alcohol, such as methanol, in the presence of an acid catalyst.
  • This etherification leads to the following advantages: increase in the octane numbers of the gasoline, because the ethers have higher octane numbers than those of the olefins which give rise to them; reduction in the olefin content of gasoline, upgrading of methanol by premium fuel without any of the problems due to free methanol.
  • ethers are MTBE (methyl tert-butyl ether) and TAME (methyl tert-amyl ether).
  • the residual methanol content at the outlet of the reactor constitutes another important problem since the introduction of free methanol into a fuel is only authorized in the presence of a co-solvent such as t-butyl alcohol.
  • the object of the present invention is to produce a cut of hydrocarbons with a high octane number.
  • light gasoline of catalytic cracking has an end point of distillation which can be between 60 and 140 ° C and therefore includes hydrocarbons having carbon atom numbers equal to 5, 6 and 7 among which olefins having a tertiary double bond on which methanol can react to give methyl t-alkyl ethers.
  • FIG. 1 The following presentation, illustrated by FIG. 1, makes it possible to better understand the invention which can be applied either to the treatment of an olefinic essence or to a mixture of olefinic essence and of C 4 cut containing isobutene.
  • the gasoline (10) is injected into a reactor 1, or an assembly including several reactors, with methanol / in an amount such that at least 70% of the methanol remaining after reaction (preferably all of this methanol) can be removed from the gasoline by hydrocarbons having a boiling point lower than that of the ether resulting from the etherification of the isoamylenes.
  • the reactor effluent, containing ethers corresponding to the etherification of isoamylenes, isohexenes and isoheptenes is sent by line 13 to a distillation column 3, so as to separate by line 14 methanol by azeotropy with hydrocarbons in C s and C 6 having a boiling point lower than that of TAME. It may be advantageous to operate this column under pressure since the methanol content in the azeotropes increases with pressure, thus making it possible to use a larger quantity of methanol at the inlet of reactor 1 and to obtain conversion of isoolefins and quantities of methanol transformed into larger ethers. From the bottom of the distillation column, part of the gasoline is drawn off through line 15 containing substantially all of the ethers formed in reactor 1 and partly or preferably freed of excess methanol.
  • This part of the petrol can be used directly as fuel.
  • This distillate is sent via line 14 to a reactor 2 so as to convert these isoolefins into ethers and to increase the quantity of methanol transformed into ether.
  • the C 5 C6 fraction of gasoline containing ethers and freed from methanol is sent via line 17 and mixed with the heavy fraction in line 16 to be used as fuel.
  • This fuel whose volume has increased as a result of the introduction of methanol valued in the form of ethers, is characterized by higher octane numbers than those of the initial gasoline.
  • the mixture is injected into reactor 1 with methanol preferably in an amount such that the excess remaining after reaction can be removed by hydrocarbons having a boiling point which makes it possible to separate them from the lightest ether, MTBE, that is to say C 4 and C 5 hydrocarbons.
  • the reactor effluent is therefore separated into a gasoline containing MTBE, TAME and the ethers corresponding to the C 6 and C 7 olefins leaving the bottom of the distillation column 3 via line 15, and into a distillate containing methanol. entrained by azeotropy with C 4 hydrocarbons and part of the C 5 hydrocarbons. This distillate containing isobutene and the unreacted isoamylenes is sent via line 14 to reactor 2.
  • the effluent from this reactor is sent to the washing section to recover the methanol which is recycled to reactor 1.
  • the effluent stripped of methanol is sent via line 18 to a distillation column 5 to be separated at the bottom in a section C 5 containing MTBE and TAME which is sent by line 7 to the fuel storage and in a distillate leaving at the top by line 9 and constituted by the cut C 4 stripped of isobutene.
  • a light gasoline of catalytic cracking whose final point of distillation is equal to 135 ° C., essentially contains C 5 , C 6 and C 7 hydrocarbons, of which 7.4% by weight of 2-methylenes-1 and 2, 4% isohexenes and 2% isoheptenes which are etherifiable by) methanol.
  • Etherification is carried out in a reactor containing a fixed bed of sulphonic resin such as AMBERLYST 15 resin (registered trademark).
  • the petrol is introduced into the reactor with methanol so that the methanol molar ratio to the sum of the etherifiable olefins is equal to 4.
  • the temperature of the reactor is maintained at 70 ° C. and the flow rate of the petrol charge + methanol is such as hvv is equal to 2.
  • the reactor effluent is sent directly to a water extraction column, operating against the current to remove the methanol which is recycled to the reactor after separation of the water by distillation.
  • quantity a increased by 4.1% by weight following the introduction of methanol in ether form contains 8.3% of TAME, 3.7% of methyl ethers of isohexenes and 1.3% of methyl ethers of isoheptenes.
  • the conversion rates of isopentenes, isohexenes and isoheptenes are respectively 80, 70 and 50%.
  • the increase in research octane number obtained by etherification of light gasoline is equal to 1.5.
  • This example shows, by comparison with Example 1, that it is possible by carrying out the etherification according to the process described in the figure, to introduce into the petrol more methanol in combined form and to obtain a petrol having a higher octane number, while having a lower quantity of gasoline to be treated by washing with water.
  • 100 parts of the light gasoline of catalytic cracking identical to that used in Example 1 and 13.8 parts of methanol are introduced into reactor 1 at 70 ° C so that the v.v.h. is equal to 3.6.
  • the methanol molar ratio on the sum of the etherifiable olefins is equal to 2.3.
  • the reactor effluent which contains residual etherifiable olefins, is sent via line 13 to the distillation column 3 operating at 8 bar abs. 56.5 parts of a gasoline stripped of methanol and which contains 95% of the etherifiable residual C 7 olefins and 3% of the etherifiable residual C 5 olefins are withdrawn from the bottom.
  • the distillate leaving at the head consists of 47 parts of light fractions of gasoline and 10 parts of methanol. It contains 97% of the etherifiable C 5 olefins and 5% of the etherifiable C 7 olefins.
  • This distillate, substantially freed of ether, is sent via line 14 to reactor 2 with a vvh equal to 2.2.
  • the reactor temperature is maintained at 70 ° C.
  • most of the remaining isoamylenes are converted to TAME with a high conversion rate due to the high methanol to isoamylene ratio (8.2) at the inlet of this reactor.
  • the reactor effluent is sent to the extraction column with water to remove the methanol (9.1 parts) which is recycled to reactor 1 after distillation in column 4.
  • the petrol free of methanol leaving the line 17 is mixed in line 15 with the gasoline drawn off at the bottom of column 3 and containing ethers and C 6 and C 7 hydrocarbons. 104.7 parts of gasoline are thus recovered.
  • the quantity of methanol 4.7 parts, introduced in the form of ethers, is greater than in the case of Example 1.
  • the overall conversion of isoamylenes is equal to 93.6%.
  • the conversions of isohexenes and isoheptenes are 65% and 40% respectively.
  • the gasoline freed from methanol leaving via line 16 contains 9.6% of TAME, 4.3% of methyl ether of isohexenes and 1% of methyl ether of isoheptenes.
  • This example shows that it is possible and even advantageous to etherify in the same unit, a light essence of catalytic cracking and a C 4 cut obtained in a catalytic cracking unit.
  • the reactor effluent, containing the etherifiable residual olefins, is sent via line 13 in column 3 operating at 8 bar abs. 105 parts of a gasoline stripped of methanol and containing MTBE, TAME and C 7 and C 8 ethers. This essence contains 99% of the etherifiable residual C 7 olefins and 2% of the residual isobutene.
  • the distillate leaving at the head (1% of the etherifiable residual C 7 olefins and 98% of the residual isobutene) consists of 90.8 parts of light hydrocarbons and 7.2 parts of methanol.
  • This distillate is sent at 70 ° C via line 14 to reactor 2 with a vvh equal to 2.4.
  • the isobutylene and the remaining isoamylenes are transformed into ethers with high conversion rates due to the high methanol to etherifiable olefin mole ratio (3.3) at the inlet of the reactor.
  • the effluent from this reactor is sent to the water extraction column to remove the methanol (5.5 parts) which is recycled to reactor 1.
  • This effluent is then sent via line 17 and then 18 to the column with distill 5 so as to separate the C 4 (62 parts) from a gasoline C s containing MTBE and TAME.
  • This gasoline C s is mixed by line 27 with the gasoline leaving column 3 through line 15. There is thus recovered 136 parts of a gasoline stripped of methanol and containing 23.4% by weight of MTBE, 7.4 % TAME, 3.3% methyl ether of isohexenes and 0.97% methyl ether of isoheptenes.
  • the overall conversion rates of isobutene, isoamylenes, isohexenes and isoheptenes are 99.6 - 87.2 - 50 and 40%, respectively.
  • the increase in the octane rating for gasoline, obtained by joint etherification of gasoline and a C 4 cut, is in this case equal to 8.
  • the quantity of methanol introduced in the form of ethers represents 11.9% of the gasoline obtained.
  • the reactor effluent is sent to the distillation column 3 operating at 8 bar abs. 30.5 parts of a fraction stripped of methanol containing 33% of MTBE, 42% of TAME, 1% of methyl ether of isohexenes, 90% of the residual etherifiable C 6 olefins and 4% of isobutene are withdrawn from the bottom. residual. At the top of the column, 85.4 parts of light fraction containing 9.3% of methanol entrained by azeotropy and the rest of the hydrocarbons are drawn off. This distillate is sent with a vvh equal to 2.1 in the reactor 2. containing the same resin maintained at 70 ° C.
  • isobutene and the non-transformed isoamylenes are etherified with methanol with high conversion rates due to the high methanol to olefins molar ratio at the inlet of the reactor.
  • the effluent from this reactor is sent to the water extraction column to remove the methanol (7.9 parts) which is recycled to reactor 1 after separation in column 4.
  • the effluent stripped of methanol is sent by lines 17 and 18 in column 5 so as to separate the C 4 (38 parts) of a gasoline containing MTBE and TAME.
  • This gasoline is mixed by line 7 with that leaving column 3 through line 15. This gives 71 parts of a gasoline stripped of methanol and containing 15% MTBE, 23.8 / A TAME and O 1 41. isohexene methyl ether.
  • the overall conversion rates of isobutene, isoamylenes and isohexenes are 99.7, 92.5 and 50%, respectively.
  • the quantity of methanol introduced in the form of ethers represents 13% of the gasoline obtained.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP85401133A 1984-07-10 1985-06-10 Verfahren zur Herstellung von einem hoch Oktan-Kohlenwasserstoffenschnitt durch Etherifierung von Olefinen Expired EP0172040B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8410978 1984-07-10
FR8410978A FR2567534B1 (fr) 1984-07-10 1984-07-10 Procede de production d'une coupe d'hydrocarbures a indice d'octane eleve, par etherification d'olefines

Publications (2)

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EP0172040A1 true EP0172040A1 (de) 1986-02-19
EP0172040B1 EP0172040B1 (de) 1987-08-05

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EP85401133A Expired EP0172040B1 (de) 1984-07-10 1985-06-10 Verfahren zur Herstellung von einem hoch Oktan-Kohlenwasserstoffenschnitt durch Etherifierung von Olefinen

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US (1) US4647703A (de)
EP (1) EP0172040B1 (de)
JP (1) JPS6136393A (de)
DE (1) DE3560415D1 (de)
FR (1) FR2567534B1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0509162A1 (de) * 1989-03-31 1992-10-21 MOBIL OIL CORPORATION (a New York corporation) Umwandlung von lichten Kohlenwasserstoffen in Ether enthaltende Benzine

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4830635A (en) * 1987-12-08 1989-05-16 Mobil Oil Corporation Production of liquid hydrocarbon and ether mixtures
US4925455A (en) * 1989-03-17 1990-05-15 Mobil Oil Corporation Process for the etherification of linear and branched olefins
US5011506A (en) * 1989-09-29 1991-04-30 Mobil Oil Corporation Integrated etherification and alkene hydration process
US5102428A (en) * 1989-10-20 1992-04-07 Mobil Oil Corporation Integrated process for the production of diisopropyl ether and gasoline
US4988366A (en) * 1989-10-24 1991-01-29 Mobil Oil Corporation High conversion TAME and MTBE production process
US5080691A (en) * 1990-04-04 1992-01-14 Mobil Oil Corp. Process for the conversion of light olefins to ether-rich gasoline
US5078751A (en) * 1990-04-04 1992-01-07 Mobil Oil Corporation Process for upgrading olefinic gasoline by etherification wherein asymmetrical dialkyl ethers are produced
GB9018719D0 (en) * 1990-08-25 1990-10-10 British Petroleum Co Plc Etherification process
FI92319C (fi) * 1992-03-18 1994-10-25 Neste Oy Menetelmä metyylieetterien valmistamiseksi
US5245087A (en) * 1992-09-30 1993-09-14 Phillips Petroleum Company Etherification process
US5413717A (en) * 1993-08-30 1995-05-09 Texaco Inc. Method of recovering MTBE from wastewater
FR2730486B1 (fr) * 1995-02-15 1997-09-05 Inst Francais Du Petrole Procede comportant l'etherification optimisee d'une coupe d'hydrocarbures contenant des olefines ayant 6 atomes de carbone par molecule
FI101220B (fi) 1995-12-22 1998-05-15 Neste Oy Menetelmä alkyylieetterien ja niiden seosten valmistamiseksi

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2411881A1 (fr) * 1977-12-16 1979-07-13 Gulf Canada Ltd Preparation d'une essence d'hydrocarbures contenant de l'ether methyl amylique tertiaire

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4193770A (en) * 1977-12-22 1980-03-18 Gulf Canada Limited Preparation of gasoline containing tertiaryamyl methyl ether
FR2455019A1 (fr) * 1979-04-24 1980-11-21 Inst Francais Du Petrole Procede de production de methyltertiobutyl ether a partir de methanol et d'isobutene

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2411881A1 (fr) * 1977-12-16 1979-07-13 Gulf Canada Ltd Preparation d'une essence d'hydrocarbures contenant de l'ether methyl amylique tertiaire

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0509162A1 (de) * 1989-03-31 1992-10-21 MOBIL OIL CORPORATION (a New York corporation) Umwandlung von lichten Kohlenwasserstoffen in Ether enthaltende Benzine

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Publication number Publication date
EP0172040B1 (de) 1987-08-05
FR2567534A1 (fr) 1986-01-17
DE3560415D1 (en) 1987-09-10
US4647703A (en) 1987-03-03
JPS6136393A (ja) 1986-02-21
FR2567534B1 (fr) 1986-12-26

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